CN1620426A - Process for preparing quaternary phenolate solutions and process for regenerating and recycling quaternary phenolate solutions from reaction mixtures - Google Patents
Process for preparing quaternary phenolate solutions and process for regenerating and recycling quaternary phenolate solutions from reaction mixtures Download PDFInfo
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- CN1620426A CN1620426A CNA028283309A CN02828330A CN1620426A CN 1620426 A CN1620426 A CN 1620426A CN A028283309 A CNA028283309 A CN A028283309A CN 02828330 A CN02828330 A CN 02828330A CN 1620426 A CN1620426 A CN 1620426A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/06—Purification or separation of guanidine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing solutions of quaternary cations and anions from deprotonated hydroxyaromatic compounds by reactive extraction of quaternary salts in an organic solvent in the presence of aqueous hydroxide solutions, hydroxyaromatic compounds and an organic solvent, and for recycling quaternary phenolate solutions from the reaction mixture.
Description
The present invention relates to a kind of in organic solvent in the presence of hydroxide aqueous solution, hydroxy aromatic compound and organic solvent, reaction, extraction by quaternary salt prepares season positively charged ion and the method for anionic solution by the hydroxy aromatic compound of deprotonation, and the method that makes the phenol quaternary salt solution recirculation in the reaction mixture.
The season positively charged ion and anionic salt, particularly phenol quaternary salt solution that is made by the deprotonation hydroxy aromatic compound can use as alkali, catalyzer or reactive component in a series of organic reactions.Because these salt commercial be not allow facilely, their raw material is relatively expensive, therefore on the one hand, needs the method for synthetic these salt, on the other hand, they need be reclaimed from reaction mixture.
DE A 19858967 has described a kind of preparation method of phenol tetrabutylammonium liquid preparation.Wherein, the phenol solution of Tetrabutyl amonium bromide is mixed with sodium phenylate, excessive phenol is removed in distillation, removes by filter Sodium Bromide then.
The shortcoming of this method is that on the one hand, the necessary steaming removed catabiotic phenol, on the other hand, is difficult to remove the Sodium Bromide that may go out with very tiny crystal settling if desired.Therefore, need a kind of simple, low cost method of design.Another purpose is to reclaim season positively charged ion phenates from reaction mixture.Therefore, this method should also provide the possibility of reaction mixture being carried out aftertreatment, so that can recycle season positively charged ion phenates solution once more.
When finishing task of the present invention, found a kind of very simple reaction, extraction method, wherein can obtain surprisingly almost quantitative reaction and even in the percentage extraction of very high organic phenol quaternary salt solution of when extraction step, and glitch-free by product.
Therefore, content of the present invention is a kind of by season positively charged ion (Q
N+) and hydroxy aromatic compound (R-(OH)
k) preparation salt (Q
N+) k[(
-O)
k-R]
nThe method of organic solution, it is characterized in that: make oxyhydroxide M
R+(OH
-)
rThe aqueous solution, at least a quaternary salt (Q
N+)
m[Y
M-]
n, R-(OH)
kThe solvent not exclusively miscible with at least a and water closely contacts, subsequently from comprising (Q
N+)
k[(
-O)
k-R]
nWith optional R (OH)
kAnd/or (Q
N+)
m[Y
M-]
nOrganic phase in isolate water.
Another content of the present invention be a kind of processing come in the reaction mixture quaternary salt and with it as salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nThe method returned of the organic solution circulation of mixture, it is characterized in that described mixture especially comprises:
1. one or more quaternary salts (Q
N+)
m[Y
M-]
n
2. a hydroxy aromatic compound R-(OH)
k, and randomly
3. one or more organic solvents,
And following the reaction:
A) make oxyhydroxide M
R+(OH
-)
rThe aqueous solution with comprise quaternary salt (Q
N+)
m[Y
M-]
nOrganic solution contact, subsequently with water from comprising (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nAnd/or R-(OH)
kOrganic phase in isolate;
B) optional carry out further post-processing step after, (the Q that will in described organic solution, comprise
N+)
k[(
-O)
k-R]
nThe R that randomly comprises (OH)
kAnd/or (Q
N+)
m[Y
M-]
nTurn back in the reaction.
Content of the present invention also comprises a kind of by season positively charged ion (Q
N+) and hydroxy aromatic compound (R-(OH)
k) preparation salt (Q
N+) k[(
-O)
k-R]
n(Q
N+)
m[Y (1)
M-]
nThe method of organic solution, it is characterized in that: make oxyhydroxide M
R+(OH
-)
rThe aqueous solution quaternary salt (Q different with at least two kinds
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nThe solvent not exclusively miscible with at least a and water closely contacts, subsequently from containing (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y (1)
M-]
nOrganic phase in isolate water.(Q here
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nBe by (Q
N+)
m[Y
M-]
nTwo kinds of different members in the chemical compound lot of definition, wherein m and p are identical or different natural numbers.Preferred m is less than p.Preferred Y (1)
M-﹠amp; Y (2)
P-Combination be halogen ion (X-) ﹠amp; Sulfate radical (SO
2- 4), bromide anion (Br especially preferably
-) ﹠amp; Sulfate radical.
Within the scope of the invention in the quaternary salt of Shi Yonging, corresponding season positively charged ion Q
N+Formula (XR normally
o +)
nCompound, wherein X represents the atom of Va or VIa family, o represents the integer of 0-4, R represents C independently of each other
6-C
18Aryl, C
7-C
18Aralkyl or C
1-C
20Alkyl, n are natural numbers.
At this, these positively charged ion ammonium, Gua, Phosphonium or sulfonium cation and optional its mixture of replacing of organic group normally for example in season.Letter n represents natural number.Also can use the oligopolymer ((n=1) R group bridge joint between two X) of n＞1, but monomer ion (n=1) is preferred.
Has organic group C
6-C
18Aryl, C
7-C
18Aralkyl or C
1-C
20The ammonium ion of alkyl, guanidinium ion, Phosphonium ion, sulfonium cation and sulfoxonium ion are suitable for using in the method for the invention.In each case, these groups can be all identical or different and even can be substituted.Per two substituting groups can be replaced by a ring, also can choose wantonly and use cationic mixture of a plurality of seasons.
Following ion can be used as example and provides: the tetramethylammonium ion, four positive second ammonium ions, four positive third ammonium ions, four positive fourth ammonium ions, two positive decyl dimethylammonium ions, two Octadecane base dimethylammonium ions, three positive decyl first ammonium ions, N-methyl-N-decyl morpholine ion, N-methyl-crassitude ion, N-(2-hydroxyl-ethyl) N-ethylpiperidine ion, benzyl three fourth ammonium ions, the phenyl trimethylammonium ion, four puratized agricultural spray ion Si Jia Phosphonium ions, four Zheng Yi Phosphonium ions, four Zheng Bing Phosphonium ions, Si Zheng Ding Phosphonium ion, two positive decyl Er Jia Phosphonium ions, two Octadecane base Er Jia Phosphonium ions, three positive Gui Ji Jia Phosphonium ions, benzyl San Ding Phosphonium ion, Ben base San Jia Phosphonium ion Si Ben Phosphonium ion, the Hexaethyl guanidinium ion, tetramethyl-dihexyl guanidinium ion.
Preferred tetraalkyl ammonium ion, four aryl ammonium ions, Si Wan Ji Phosphonium ion, Si Fang Ji Phosphonium ion and the six alkyl guanidine ions of using.Tetrabutylammonium ion or four puratized agricultural spray ions and Si Ding Phosphonium ion or Si Ben Phosphonium ion are preferred especially the uses, more preferred tetrabutylammonium ion or Si Ben Phosphonium ion.
For example, halogen negatively charged ion, nitrate radical, sulfate radical, bisulfate ion, carbonate, bicarbonate radical, phosphate radical, hydrogen phosphate, dihydrogen phosphate, tetrafluoroborate, perchlorate, carboxylate radical or hexafluoro-phosphate radical can be used as cationic pair anion Y of season
M-Letter m represents natural number.The mixture of different anions is possible.The halogen negatively charged ion is preferred, especially preferably bromine anions.
Six alkyl halide guanidines, quaternary alkylammonium halides and four aryl phosphonium halides are preferred, especially preferably Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-phenyl phosphonium bromide and four butyl phosphonium bromides.The content of this quaternary salt for example, in the weight of reaction mixture, can be between 0.01-30 weight %.The content of quaternary salt is preferably between 0.5-15 weight %, particularly preferably in 1-5 weight %.
The aromatic hydroxy compound R-(OH) that can react by the present invention
kWherein R represents aromatic group, k represents the integer of 0-4, is preferably selected from aromatic substance (k=2) or the polyhydroxylated aromatic substance (2＜k＜=4) or the bis-phenol (k=2) of monohydroxylated aromatic substance (k=1), dihydroxy, and it can have 0-4 and be selected from C
1-C
18Alkyl or cycloalkyl, C
6-C
18Aryl, C
7-C
18Aralkyl, C
1-C
18The substituting group of alkoxyl group, fluorine, chlorine or bromine.Alkyl, aryl and aralkyl substituting group itself can also be substituted or can carry functional group for example ether, thioether group, ketone group, epoxy group(ing), halogen, heterocycle.The aromatic substituent ring can be thick and or bridging, a plurality of groups can be joined together to form ring.
Example is a monohydroxy compound; phenol for example; adjacent; between or p-cresol; adjacent; between or para-chlorophenol; adjacent; between or p-ethyl phenol; adjacent; between or the n-propyl phenol; adjacent; between or p-tert-butylphenol; adjacent; between or to isooctyl phenol; adjacent; between or to stearyl-phenol; 2; 4; 6-three cresols; adjacent; between or p-phenyl phenol; adjacent; between or to cyclohexylphenol; adjacent; between or p methoxy phenol; 2; the 6-xylenol; 2; the 4-xylenol; 3; the 4-xylenol; the 1-naphthols; beta naphthal or two-or polyol for example Resorcinol and quinhydrones; and bis-phenol for example 2; 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane); 2; 2-two (3; 5-dimethyl-4-hydroxyphenyl) propane; 1; 1-two (4-hydroxy phenyl) hexanaphthene; 1; 1-two (4-hydroxyphenyl)-3; 3; 5-trimethyl-cyclohexane (bis-phenol TMC); α; α-two (4-hydroxyphenyl)-m-diisopropyl benzene; 6; 6 '-dihydroxyl-3; 3; 3 '; 3 '-tetramethyl--1,1 '-spiral shell-(two) 1,2-indane; 4; 4 '-dihydroxybiphenyl or 2,4 '-dihydroxybiphenyl.
Can also use the mixture of various aromatic hydroxy compounds.Monohydroxy compound is preferred the use, especially preferably uses phenol.
Only with water section miscible and the material that uses is inert simple substance or mixture can be used as organic solvent and use.The boiling point of solvent is preferably between about 40-200 ℃.In addition, preferred specific inductivity is less than about 25, the solvent of preferred especially specific inductivity＜15.Can comprise inert solvent in the mixture, with R-(OH)
kMeter, the content of inert solvent is 0-99 weight %, is preferably 20-98 weight %, is preferably 40-98 weight % especially.Compare R-(OH) under obvious metachemistry calculated amount with reaction yield
kThe component that oneself can be used as solvent mixture is used.
What can be used as that solvent uses is for example chlorobenzene, dichlorobenzene, fluorobenzene, benzene,toluene,xylene, methyl-phenoxide, hexanaphthene, sherwood oil, methylene dichloride, chloroform or 1 of hydrocarbon, halohydrocarbon and aromatic solvent for example, the 2-ethylene dichloride, dipolar aprotic solvent is N,N-DIMETHYLACETAMIDE, acetonitrile, N-Methyl pyrrolidone, ester, the ether ethylene glycol of diox, tetrahydrofuran (THF), t-butyl methyl ether and etherificate for example for example, particularly preferably is chlorobenzene.
M
R+(OH
-)
rRepresent the oxyhydroxide of one or more periodic table of elements Ia (r=1) or IIa (r=2) family.Its example is lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide.Potassium hydroxide, sodium hydroxide and calcium hydroxide are preferred, especially preferably sodium hydroxide.M
R+(OH
-)
rCan be metered in the extraction mixture with the aqueous solution or suspension, perhaps it can be used as solid and adds with water, and wherein the former is preferred.Preferable methods is that the pH value that contained water before extracting is 7 to 14, especially preferably about 9 to 13.5.
The embodiment of using preferred, particularly preferred or most preferred parameter, compound, definition and explanation is preferred, particularly preferred or most preferred.
But, above-mentioned general definition, parameter, compound and explanation or in preferable range, mention those can make up mutually, that is to say, can between scope and preferable range, make up in each case.
(Q of the present invention
N+)
k[(
-O)
k-R]
nThe preparation method preferably at [R-(OH)
k]/[M
R+(OH
-)
r] mol ratio greater than about 1.1[r/k] under carry out add R-(OH) because be surprisingly found out that metachemistry calculated amount ground
kProductive rate to reaction, extraction has active influence.Preferred especially this method is at [R-(OH)
k]/[M
R+(OH
-)
r] mol ratio greater than about 3.1[r/k] under carry out.
According to the requirement of organic solution, (the Q of about 1-99.9%
N+)
m[Y
M-]
nCan be converted into (Q
N+)
k[(
-O)
k-R]
nBe surprisingly found out that unreacted (Q
N+)
m[Y
M-]
nBe extracted in the organic phase together too.When for example in subsequent reaction, (Q
N+)
m[Y
M-]
nWhen being used as phase-transfer catalyst or conducting salt, this is desirable fully.Therefore, content of the present invention also is both to comprise (Q
N+)
k[(
-O)
k-R]
nAlso comprise (Q
N+)
m[Y
M-]
nOrganic solution.
According to (the Q in organic phase
N+)
k[(
-O)
k-R]
nWith (Q
N+)
m[Y
M-]
nIdeal ratio, oxyhydroxide M
N+(OH
-)
r/ (Q
N+)
m[Y
M-]
nRatio be about 0.05[m/r]-5[m/r].If there is excessive R-(OH)
k, so when ratio increases, (the Q of generation
N+)
k[(
-O)
k-R]
nQuantity increase.Astoundingly, for conversion almost completely, about 1[m/r] ratio in most of the cases be enough.Higher ratio often cause in most of the cases the M of unwanted higher organic solution
R+Content.
High M
R+Content is undesirable in commercial run, because contain M
R+Salt the solubleness in organic solution is very poor usually, and can in reactor, separate out uncontrollably.
Find the M of solution prepared according to the methods of the invention surprisingly
R+Content is less than about 20ppm.M
R+Content is preferred less than the solution of about 10ppm, M
R+Content is particularly preferred less than the organic solution of about 5ppm.Equally under the situation of the oxyhydroxide that adds the metachemistry calculated amount, promptly at M
R+(OH
-)
r/ (Q
N+)
m[Y
M-]
nRatio greater than about 1[m/r] time, do not have the obviously (M of amount astoundingly
R+)
k[(
-O)
k-R]
rBe extracted in the organic phase.
The organic solution that is obtained according to its water-retaining capacity the extraction after by water saturation.If use it for (wherein glassware for drinking water has interference effect) in the reaction, then must carry out drying to it before use.For this reason, can adopt the known method of professional for example through anhydrous salt drying, gas carry, molecular sieve, component distillation.
By (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nThe organic solution of forming is necessary when the direct carbonylation of phenol and carbon monoxide and oxygen prepares diphenyl carbonate for example.Therefore, content of the present invention is the application of organic solution of the present invention in oxidation carbonylation.
The volume ratio of organic aqeous phase can be selected in very wide scope; For contacting and the reason of actually operating, difference can not be too big, therefore the volume ratio preferably about 0.01 to 100 of organic aqeous phase.The volume that has been found that water produces favorable influence to being extracted into less in the organic phase, reduced wastewater flow rate in addition as far as possible.Therefore the phase ratio of preferred especially organic aqeous phase is about 0.5 to 80, most preferably is about 2 to 50.
Water can comprise ionogen in addition, for example the halogen of basic metal or alkaline-earth metal.Be surprisingly found out that (M
R+)
m[Y
M-]
rExistence in addition to (Q
N+)
k[(
-O)
k-R]
nThe productive rate of solution also produces advantageous effect.Therefore preferred scheme is to carry out in the presence of electrolytical additional, and particularly preferred scheme is at negatively charged ion Y
M-The existence of metal-salt under carry out, most preferred scheme this at (M
R+)
m(Y
M-)
rExistence under carry out.
In the method for the invention, for aftertreatment with recycle salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nOrganic solution, for example, can use commercial available Tetrabutyl amonium bromide to come the synthesizing phenol tetrabutylammonium.
In the oxidation direct carbonylation of phenol, for example, the phenol tetrabutylammonium is used as phenates alkali (Q
N+)
k[(
-O)
k-R]
n, and Tetrabutyl amonium bromide is used as quaternary salt (Q
N+)
m(Y
M-)
nBecause during reaction,, therefore make phenates alkali (Q perhaps at the part or all of protonation reaction of post-processing stages for example because the carbonic acid gas phenates that forms as by product is consumed
N+)
k[(
-O)
k-R]
nRegeneration become the vital task of the inventive method.Method of the present invention can make during aftertreatment, generate except that other component, comprise unreacted hydroxy aromatic compound (R-(OH) usually
k), season bromide (Q
N+)
m[Y
M-]
nWith all or part of season phenates that is converted into of the logistics of solvent.
Method of the present invention can be carried out like this, that is, logistics is separated, and only have the part logistics to be transformed wholly or in part to carry out the regeneration of alkali.Perhaps, whole logistics can also with the M for phenates desired quantity aequum
R+(OH
-)
rReaction.Because find surprisingly, just under substoichiometric condition, i.e. M
R+(OH
-)
r/ (Q
N+)
m[Y
M-]
nRatio less than 1[m/r] time, with M
R+(OH
-)
rAmount, this conversion almost is to carry out quantitatively, so phenol quaternary salt aequum can be regulated with comparalive ease.This method also can be carried out so so, in order to cover the loss, only is metered into (Q in the reaction feed
N+)
m[Y
M-]
n, and (Q
N+)
k[(
-O)
k-R]
nLoss remedies by reaction of the present invention fully.
Because described solution is water saturated after extraction, in step b) it to be carried out drying before the use in the reaction of interference effect be significant so have at glassware for drinking water.Can carry out the aftertreatment of other type before equally in returning reaction, for example steaming desolventizes, and separates R-(OH)
k, remove residual metallic (for example by ion-exchange or precipitation), evaporation, precipitation or salt (Q
N+)
k[(
-O)
k-R]
nRecrystallize.
In step a), generate the Y that comprises transform portion
M-Water.If this is a kind of valuable negatively charged ion, for example PF
6 -Or bromide, be worth so this negatively charged ion is carried out aftertreatment, for example, make it be converted into volatile matter by precipitation, then undertaken by distillation, evaporating solns or other method.
When this reaction mixture middle part subpackage contained water-soluble by product, method of the present invention can be used for these components in addition and carries out enrichment.In addition, metal-salt for example can be used as those that catalyst component exists in reaction mixture, is split into to contain aqueous phase when extraction, and this makes that for ecology or economic cause they being carried out significant aftertreatment becomes possibility.In addition, can utilize the precipitin reaction of metal-salt that it is isolated for this reason.Under extraction conditions, some metal ions are separated out with oxyhydroxide.Contain Y
M-If precipitation or Y
M-Be many protonic acids negatively charged ion, contain by Y so
M-The Y ' that deprotonation generates
(m+1)-Or Y "
(m+1)-Precipitation (Y for example
M-=dihydrogen phosphate, m=1, Y '
(m+1)-=hydrogen phosphate radical, Y "
(m+1)-=phosphate radical) also is possible, and can be used for separating metal if desired.The volume ratio of organic aqeous phase changes in very wide scope; Because contact and actual operability, they can not be too inconsistent, the volume ratio of therefore preferred organic aqeous phase is about 0.01 to 100.For the reason of mentioning, the phase ratio of organic aqeous phase is preferably about 0.5 to 80, most preferably is about 2 to 50.
Contain water and can comprise ionogen, for example halogenide of basic metal or alkaline-earth metal in addition.This can be to (Q
N+)
k[(
-O)
k-R]
nThe productive rate of-solution produces favorable influence, and is preferred scheme therefore.Particularly preferably be to adopt (the M that also produces simultaneously as product
R+)
m(Y
M-)
rAs this additional ionogen.Preferably after extraction, by circulation this is contained water and partly be used to the incoming flow that extracts for this reason, perhaps always be to use the identical water that contains, therefrom only remove and comprise (M
R+)
m(Y
M-)
rWashing fluid, and to wherein being metered into additional M
R+(OH
-)
rStream.By (the M that in extraction, therefore forms
R+)
m(Y
M-)
rHold-up to R (OH)
k, (Q
N+)
m[Y
M-]
n(Q
N+)
k[(
-O)
k-R]
nDistribution equilibrium produce favorable influence, and make the loss and the wastewater flow rate that contain aqueous phase reduce to minimum.
Select ground fully, as (the M of product generation
R+)
m(Y
M-)
rSeparated and draw off as solid when surpassing solubility product.
(Q of the present invention
N+)
k[(
-O)
k-R]
nWorking method preferably at [R-(OH)
k]/[M
R+(OH
-)
r] mol ratio greater than about 1.1[r/k] under carry out add R-(OH) because be surprisingly found out that metachemistry calculated amount ground
kProductive rate to reaction, extraction has active influence.Preferred especially this method is at [R-(OH)
k]/[M
R+(OH
-)
r] mol ratio greater than about 3.1[r/k] under carry out.
The ratio M of employed oxyhydroxide and quaternary salt
R+(OH
-)
r/ (Q
N+)
m[Y
M-]
nAccording to (Q required in the organic phase
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nRatio can be at about 0.01[m/r]-5[m/r] between.If there is the R-(OH) of q.s
k, so when this ratio raises, (the Q of generation
N+)
k[(
-O)
k-R]
nAmount also increase astoundingly,, about 1[m/r for conversion almost completely] ratio in most of the cases be enough.Therefore, M
R+(OH
-)
r/ (Q
N+)
m[Y
M-]
nRatio at about 0.1[m/r]-1.5[m/r] scope in be preferred.The M of the higher organic solution that higher ratio often causes in most of the cases not needed
R+Content, and cause more R-(OH)
kLoss.
Method of the present invention need be at R-(OH)
kThere is preparation product down; Excessive R-(OH)
kHelp preparing this solution.Although method of the present invention can be used, be to use R-(OH) in multiple reaction
kReaction as raw material is preferred.Reaction product is that a kind of organic ester is for example by R-(OH) in addition
kThe reaction of the ester that obtains is preferred, particularly preferably is carbonic acid and R-(OH)
kEster diphenyl carbonate for example.
Find surprisingly, in post-treating method of the present invention, the M of the solution of prepared in accordance with the method for the present invention
R+Content is less than about 20ppm.M
R+Content is preferred less than the solution of about 10ppm, particularly preferably is M
R+Content is less than the organic solution of about 5ppm.
The 3rd content of the present invention is that selectivity prepares salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y (1)
M-]
nThe method of organic solution because find surprisingly, at two kinds of quaternary salt (Q
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nMixture in, (Q
N+)
p[Y (2)
P-]
nWith oxyhydroxide M
R+(OH
-)
rReaction have high selectivity.At this, (Q
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nBe by (Q
N+)
m[Y
M-]
nTwo kinds of different members in the chemical compound lot of definition, wherein m and p are identical or different natural numbers.Preferred m is less than p.Preferred combination Y (1)
M-﹠amp; Y (2)
P-Halogen ion (X
-) ﹠amp; Sulfate radical (SO
4 2-), bromide anion (Br especially preferably
-) ﹠amp; Sulfate radical.
According to the selected stoichiometric quantity of compound, can prepare and contain (Q
N+)
k[(
-O)
k-R]
n, (Q
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nOrganic solution, (Q wherein
N+)
m[Y (1)
M-]
n/ (Q
N+)
p[Y (2)
P-]
nMolar ratio compare with initial ratio significantly and to increase.The another kind of selection is to prepare a kind of (Q that almost do not have
N+)
p[Y (2)
P-]
nAnd only by quaternary salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y (1)
M-]
nThe solution of forming.In this case, whole (Q of consumptions almost
N+)
m[Y (1)
M-]
nAll be extracted in the organic phase, perhaps part (Q
N+)
m[Y (1)
M-]
nEqually can with M
R+(OH
-)
rBe converted into (Q together
N+)
k[(
-O)
k-R]
n
Selectivity prepares the method for phenol quaternary salt and can also advantageously use in the aftertreatment of reaction mixture.For example, in the reaction of needs organic soluble bromine source and phenates alkali, can remedy the loss of phenates by method of the present invention.In this case, do not need to use expensive bromide as raw material, but can be metered into vitriol, it optionally is converted into phenates, in this case, does not produce the loss of a large amount of bromide source.
Extraction of the present invention can one the step in, carry out in the multistep or in a continuous manner.In most of the cases successive for example counter-current extraction be preferred.
Preparation of the present invention and post-treating method are under-10-200 ℃ temperature, preferably under 10-130 ℃ temperature, particularly preferably under 20-90 ℃ the temperature and under the pressure of 0.1-200 crust, preferably under the pressure of 0.5-50 crust, carry out under the pressure particularly preferably in the 1-10 crust.
For method of the present invention, can adopt abstraction technique, this technology for example is described in KIRK-OTHMER, Encyclopedia of Chemical Technology, the 4th edition, Volume 10,1993, the 25-181 pages or leaves and Ullmann ' s Encyclopedia ofIndustrial Chemistry, the 5th edition, the B3 volume, Unit Operations II, 1988, Kapitel 6, Liquid-Liquid-Extraktion, 6-1 to 6-61 page or leaf.
In order to implement method of the present invention, can use the extraction equipment of following type, for example tower, tower, tower, mixer-settlers, mixing nozzle and precipitation apparatus and the centrifugal extractor of type of noenergy input with rotational structure with pulse liquid or pulse member.
The example of the tower of noenergy input is spray tower, packing tower and sieve-tray tower, and they are different disperseing mutually.
Example with tower of pulse liquid or pulse member is pulsed sieve plate column, pulsed packed tower (band piston-type pump, band is according to the pulser of Misek or Wepuko), according to the tower of Prochazka or Karr band oscillating screen plate.
Example with tower of rotation internal structure is rotating disc contactor (RDC), asymmetric rotating disc formula extractor (ARD), Ao Erdexiu-La Shidun multi-level mixer tower, K ü hni extractor, Scheibel tower, SHE extractor and Graesser contactor.
The example of mixer-settlers is Davy McKee mixer-settlers, the tower extractor of Lurgi, IMI, normal mill and according to the Box type mixer-settlers of Denver.
The example of centrifugal extractor is centrifugal extractor of Podbielniak and the centrifugal extractor of Robatel.
Here extractor can be with the extractor of single extractor, parallel connection or the extractor running of serial connection.When using the extractor of serial connection, a kind of or dissimilar extractors can turn round in a tandem simultaneously.Each can be in the same way in tandem or preferably countercurrent flow.
Those of ordinary skills know that equally method of the present invention depends on material R-(OH)
k, (Q
N+)
m[Y
M-]
nWith the chemical property of solvent LM, and according to partition ratio and required separation efficiency, this extraction must have being suitable for particular separation theory problem stage number and having the reaction, extraction of meeting dynamic (dynamical) duration of contact of certain number.
Yet usually preferred this extraction is carried out in one mixer-settlers, because extraction yield in most of the cases is gratifying.
Embodiment
Extraction is undertaken by halfhour approximately phase shaking out.Organic mutually aqeous by means of gas Chromatographic Determination after using acetone and internal standard is diluted subsequently, to measure each component concentrations.At this, prove Tetrabutyl amonium bromide (TBAB ,=(Q
N+)
m[Y
M-]
n) be decomposed into Tributylamine and butyl bromide.Phenol tetrabutylammonium (TBAP ,=((Q
N+)
k[(
-O)
k-R]
n) can obtain by the ratio calculation of Tributylamine and butyl bromide with the ratio of Tetrabutyl amonium bromide; Can obtain the extraction yield of organic phase by the content that contains the Tributylamine in water (AP) and the organic phase (OP).Concentration numerical value in the table is to carry out reaction, extraction value before
Embodiment 1
Under 80 ℃, in each case, with 31.5g Tetrabutyl amonium bromide and the 15g phenol of 50 gram KOH aqueous solution simple extractions in the 250ml chlorobenzene.The result is described in the table 1.
Table 1
| KOH concentration [weight %] among the AP | 5.48 | ?6.02 | ?6.58 | ?7.12 | ?8.24 | ?10.98 | ?16.46 |
| The KOH/TBAB ratio | 0.5 | ?0.55 | ?0.6 | ?0.65 | ?0.75 | ?1 | ?1.5 |
| With TBA +The TBAP productive rate (%) of meter | 49.0 | ?54.2 | ?55.8 | ?60.0 | ?61.6 | ?69.6 | ?95.0 |
| TBA among the OP +Extraction yield (%) | 97.3 | ?97.6 | ?97.3 | ?97.3 | ?97.8 | ?97.7 | ?98.8 |
Embodiment 2
Under 80 ℃, in each case, with 31.5g Tetrabutyl amonium bromide and the 15g phenol of 250 gram KOH aqueous solution simple extractions in the 250ml chlorobenzene.The result is described in the table 2.
Table 2
| KOH concentration [weight %] among the AP | 1.09 | ?1.65 |
| The KOH/TBAB ratio | 0.5 | ?0.75 |
| With TBA +The TBAP productive rate (%) of meter | 36.9 | ?61.9 |
| TBA among the OP +Extraction yield (%) | 73.1 | ?71.5 |
Embodiment 3
Under 80 ℃, in each case, with 31.5g Tetrabutyl amonium bromide and the 55g phenol of 50 gram NaOH aqueous solution simple extractions in the 250ml chlorobenzene.The result is described in the table 3.
Table 3
| NaOH concentration [weight %] among the AP | 3.92 |
| The ratio of phenol/NaOH | 6 |
| The NaOH/TBAB ratio | 0.5 |
| With TBA +The TBAP productive rate (%) of meter | 51.8 |
| TBA among the OP +Extraction yield (%) | 100 |
Embodiment 4
Under 80 ℃, with 40 and 80 gram NaOH aqueous solution simple extraction 18.27g Tetrabutyl amonium bromide and the solution of 381.73g phenol in chlorobenzene.The result is described in the table 4.
Table 4
| NaOH concentration [weight %] among the AP | 2.74 | ?1.39 | ?2.74 | ?1.39 |
| The ratio of phenol/NaOH | 25 | ?25 | ?1 | ?1 |
| The NaOH/TBAB ratio | 0.5 | ?0.5 | ?0.5 | ?0.5 |
| With TBA +The TBAP productive rate (%) of meter | 52.9 | ?50.0 | ?48.6 | ?40.8 |
| TBA among the OP +Extraction yield (%) | 100 | ?99.9 | ?60.7 | ?33.3 |
Sodium content in the organic phase all is lower than determination limit 5ppm in all samples.
Embodiment 5
Under 80 ℃, with the NaOH and solution simple extraction 18.27g Tetrabutyl amonium bromide and the 66.6g phenol in 379.1g chlorobenzene in of NaBr in 40 gram water of different amounts.The result is described in the table 5.
Table 5
| NaOH concentration [weight %] among the AP | 5.36 | 4.71 | ?10.18 | ?9.00 | ?3.79 | ?3.17 | ?2.73 |
| NaBr concentration [weight %] among the AP | 0 | 12.1 | ?0 | ?11.6 | ?29.3 | ?40.8 | ?49.1 |
| The ratio of phenol/NaOH | 12.5 | 12.5 | ?6.25 | ?6.25 | ?12.5 | ?12.5 | ?12.5 |
| The NaOH/TBAB ratio | 1 | 1 | ?2 | ?2 | ?1 | ?1 | ?1 |
| With TBA +The TBAP productive rate (%) of meter | 97.0 | 97.6 | ?98.9 | ?99.4 | ?96.6 | ?97.7 | ?97.5 |
| TBA among the OP +Extraction yield (%) | 99.9 | 100. 0 | ?99.9 | ?99.9 | ?100. ?0 | ?100. ?0 | ?100. ?0 |
| The content of sodium [ppm] among the OP | ＜0.2 | 0.3 | ?50 | ?110 | ?1.4 | ?6 | ?26 |
| The content of phenol [weight %] among the AP | 1.9 | 1.26 | ?3.25 | ?1.88 | ?0.82 | ?0.52 | ?0.40 |
| The content of water [weight %] among the OP | ?0.62 | ?0.51 | ?0.41 |
Embodiment 6
Under 20 ℃, mixed water extraction 10.0g Tetrabutyl amonium bromide, 11.0 gram tetrabutyl ammonium sulfate, 90g chlorobenzene and the 20.7g phenol of 1.52 gram solid NaOH with 25g.The result is summarised in the table 6.
Table 6
| NaOH concentration [weight %] among the AP | 5.64 |
| The ratio of phenol/NaOH | 5.8 |
| ?NaOH/TBA +Ratio | 0.55 |
| ?NaOH/(TBA) 2SO 4 | 2 |
| With TBA +The TBAP productive rate (%) of meter | 52.0 |
| With TBA +The TBAB " productive rate " of meter (%) | 48.0 |
| TBA among the OP +Extraction yield (%) | 100 |
The weight of this organic phase is 128.7 grams, and wherein the content of vitriol is 69mg/kg, and the content of bromine is 1.8%.Contain aqueous phase and comprise 9% vitriol.
Embodiment 7
Under 20 ℃, mixed water extraction 10.0g Tetrabutyl amonium bromide, 11.05 gram tetrabutyl ammonium sulfate, 90g chlorobenzene and the 10.0g phenol of 2.76 gram solid NaOH with 29g.The result is summarised in the table 7.
Table 7
| NaOH concentration [weight %] among the AP | 8.69 |
| The ratio of phenol/NaOH | 1.5 |
| ?NaOH/TBA +Ratio | 1.0 |
| ?NaOH/(TBA) 2SO 4 | 3.63 |
| With TBA +The TBAP productive rate (%) of meter | 81.0 |
| With TBA +" TBAB " productive rate (%) of meter | 19.0 |
| TBA among the OP +Extraction yield (%) | 96.2 |
The weight of this organic phase is 120.6 grams, and wherein the content of bromine is 1.3%, and the content of vitriol is lower than 0.01% measuring limit.The bromine content that contains water is 2.79%, and the content of vitriol is 5.9%.
Embodiment 1 shows that TBAB is converted into the productive rate of TBAP and can controls by the amount of oxyhydroxide.Astoundingly, be 0.5 o'clock in the ratio of KOH/TBAB, this reaction is carried out in quantitative productive rate (with oxyhydroxide) almost.In only extraction step, two kinds of quaternary salts (Tetrabutyl amonium bromide, tetrabutyl ammonium phenate) almost are transported in the organic phase quantitatively.
Embodiment 2 proofs, when the phase ratio of organic aqeous phase changed, not only the transformation efficiency of phenolate but also extraction yield all significantly worsened.
Embodiment 3 and 4 shows, when phenol concentration improves with season ion (TBA
+) productive rate and the extraction yield of TBAP of total amount meter all increase.
Embodiment 5 proofs, the adding of Sodium Bromide astoundingly can't produce adverse influence to the formation of TBAP, and the sodium amount that enters astoundingly in the organic phase is low-down.Contain aqueous phase on the contrary astoundingly and absorbed a spot of phenol, and the water content in the organic phase also reduces astoundingly.
Embodiment 6 shows, following situation is possible, promptly in the mixture of sulfuric acid quaternary salt and bromination quaternary salt, the reaction preference of sulfuric acid quaternary salt Pyrogentisinic Acid salt is very high when accurately regulating the stoichiometric quantity of oxyhydroxide, and is extracted in the organic phase with unreacted bromination quaternary salt almost.
Embodiment 7 shows, when the content of oxyhydroxide was the metachemistry calculated amount with respect to the content of vitriol, additionally the part bromide was converted into phenolate.Because disadvantageous phenol/this conversion of NaOH ratio and extraction are not quantitative.
Claims (10)
1. one kind by season positively charged ion (Q
N+) and hydroxy aromatic compound (R-(OH)
k) preparation salt (Q
N+)
k[(
-O)
k-R]
nThe method of organic solution, it is characterized in that: make oxyhydroxide M
R+(OH
-)
rThe aqueous solution, at least a quaternary salt (Q
N+)
m[Y
M-]
n, R-(OH)
kThe solvent not exclusively miscible with at least a and water closely contacts, subsequently from comprising (Q
N+)
k[(
-O)
k-R]
nWith optional R (OH)
kAnd/or (Q
N+)
m[Y
M-]
nOrganic phase in isolate and contain water, wherein
Q
N+Represent six alkyl guanidine ions or formula (XR
o +)
n, wherein X represents the atom of Va or VIa family, and o represents the integer of 1-4, and R represents C independently of each other
1-C
18Alkyl or cycloalkyl, C
7-C
18Aralkyl, C
6-C
18Aryl, and per two substituent group R can be by a ring replacement, and n represents natural number,
Y
M-Comprise one or more members that are selected from the group of forming by halide ion, nitrate radical, sulfate radical, bisulfate ion, phosphate radical, hydrogen phosphate, dihydrogen phosphate, perchlorate, bicarbonate radical or carbanion, chloride of preferred package or bromine root, wherein m represents natural number
At R-(OH)
kIn, R represents aromatic group, k represents the integer of 0-4,
The mixture of solvent or solvent only part is blendable with water, and is inertia concerning reactant,
M
R+(OH
-)
rOne or more oxyhydroxide of expression periodic table of elements Ia (r=1) or IIa (r=2) family.
One kind the quaternary salt that comes reaction mixture carried out aftertreatment and with it as salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nThe organic solution of mixture turn back to method in this reaction, it is characterized in that: wherein mixture comprises one or more quaternary salts (Q
N+)
m[Y
M-]
n, a kind of hydroxy aromatic compound R-(OH)
kRandomly one or more organic solvents, and following the reaction:
A) make oxyhydroxide M
R+(OH
-)
rThe aqueous solution and comprise quaternary salt (Q
N+)
m(Y
M-)
nOrganic solution closely contact, will contain water subsequently from comprising (Q
N+)
k[(
-O)
k-R]
n, (Q
N+) m[Y
M-]
nAnd/or R-(OH)
kOrganic phase in isolate;
B) optional carry out further post-processing step after, (the Q that will in organic solution, comprise
N+)
k[(
-O)
k-R]
nThe R that randomly comprises (OH)
kAnd/or (Q
N+)
m[Y
M-]
nTurn back in the reaction, wherein (Q
N+), Y
M-, M
R+, r, m, n, R-(OH)
k, (
-O)
k-R and k have the implication in the claim 1.
3. by a kind of season positively charged ion (Q
N+) and a kind of hydroxy aromatic compound (R-(OH)
k) preparation salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y (1)
M-]
nThe method of organic solution, it is characterized in that: make oxyhydroxide M
R+(OH
-)
rThe aqueous solution quaternary salt (Q different with at least two kinds
N+)
m[Y (1)
M-]
n(Q
N+)
p[Y (2)
P-]
nThe solvent not exclusively miscible with at least a and water closely contacts, and will contain water subsequently from comprising salt (Q
N+)
k[(
-O)
k-R]
n(Q
N+)
m[Y
M-]
nOrganic phase in isolate (Q wherein
N+), Y
M-, M
R+, r, m, n, R-(OH)
k, (
-O)
k-R and k have the implication in the claim 1, and p is a natural number.
4. the method for one of claim 1-3, wherein R-(OH)
kWith oxyhydroxide Mr
+(OH
-)
rBetween mol ratio [R-(OH)
k]/[M
R+(OH
-)
r] greater than about 1.1[r/k].
5. the method for one of claim 1-3, wherein M
R+(OH
-)
rWith (Q
N+)
m[Y
M-]
nRatio be about 0.05[m/r]-3[m/r].
6. the method for one of claim 1-3, wherein M in the organic solution
R+Content less than about 20ppm.
7. the method for one of claim 1-3, wherein Q
N+Represent at least a positively charged ion that is selected from the An, Phosphonium, guanidine or the sulfonium cation that are replaced by organic group.
8. the method for claim 2, wherein said reaction are the reactions of preparation diphenyl carbonate, and M
R+(OH
-)
rExpression NaOH, R-(OH)
kExpression phenol, and at least one Y
M-Expression bromine radical ion.
9. the method for one of claim 1-3 wherein extracts mixture and comprises at least a additional ionogen.
10. the method for claim 9, wherein additional electrolytical content is reused by the part of the extract aqueous solution and is regulated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10164142.7 | 2001-12-27 | ||
| DE10164142A DE10164142A1 (en) | 2001-12-27 | 2001-12-27 | Process for the preparation of quaternary salt phenolate solutions and for the regeneration and recycling of quaternary salt phenolate solutions from reaction mixtures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1620426A true CN1620426A (en) | 2005-05-25 |
| CN1307151C CN1307151C (en) | 2007-03-28 |
Family
ID=7710988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028283309A Expired - Fee Related CN1307151C (en) | 2001-12-27 | 2002-12-19 | Process for preparing quaternary phenolate solutions and process for regenerating and recycling quaternary phenolate solutions from reaction mixtures |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6727393B2 (en) |
| EP (1) | EP1461312A1 (en) |
| JP (1) | JP2005526707A (en) |
| KR (1) | KR20040068983A (en) |
| CN (1) | CN1307151C (en) |
| AU (1) | AU2002367099A1 (en) |
| DE (1) | DE10164142A1 (en) |
| TW (1) | TWI272266B (en) |
| WO (1) | WO2003055849A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104114252B (en) * | 2012-02-14 | 2017-05-10 | 荒川化学工业株式会社 | method for removing quaternary salt |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1381272A (en) * | 1971-01-26 | 1975-01-22 | Glaxo Lab Ltd | Cephalosporin compounds |
| DE19730022A1 (en) * | 1997-07-11 | 1999-01-14 | Bayer Ag | Process for the preparation of tetrabutylammonium phenolate diphenol adduct |
| DE19858967C1 (en) * | 1998-12-21 | 2000-07-13 | Bayer Ag | Liquid formulation of tetrabutylammonium phenolate |
| EP1249018B1 (en) * | 1999-12-21 | 2005-05-11 | Lockstream Corp. | Digital content security |
-
2001
- 2001-12-27 DE DE10164142A patent/DE10164142A1/en not_active Withdrawn
-
2002
- 2002-12-16 US US10/319,974 patent/US6727393B2/en not_active Expired - Fee Related
- 2002-12-19 CN CNB028283309A patent/CN1307151C/en not_active Expired - Fee Related
- 2002-12-19 EP EP02805767A patent/EP1461312A1/en not_active Withdrawn
- 2002-12-19 AU AU2002367099A patent/AU2002367099A1/en not_active Abandoned
- 2002-12-19 JP JP2003556381A patent/JP2005526707A/en not_active Withdrawn
- 2002-12-19 KR KR10-2004-7010038A patent/KR20040068983A/en not_active Application Discontinuation
- 2002-12-19 WO PCT/EP2002/014570 patent/WO2003055849A1/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| US20030151019A1 (en) | 2003-08-14 |
| JP2005526707A (en) | 2005-09-08 |
| DE10164142A1 (en) | 2003-07-10 |
| CN1307151C (en) | 2007-03-28 |
| EP1461312A1 (en) | 2004-09-29 |
| AU2002367099A1 (en) | 2003-07-15 |
| TW200306302A (en) | 2003-11-16 |
| WO2003055849A1 (en) | 2003-07-10 |
| US6727393B2 (en) | 2004-04-27 |
| KR20040068983A (en) | 2004-08-02 |
| TWI272266B (en) | 2007-02-01 |
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